JP7030820B2 - Method for producing hydrogen cyanide - Google Patents
Method for producing hydrogen cyanide Download PDFInfo
- Publication number
- JP7030820B2 JP7030820B2 JP2019537883A JP2019537883A JP7030820B2 JP 7030820 B2 JP7030820 B2 JP 7030820B2 JP 2019537883 A JP2019537883 A JP 2019537883A JP 2019537883 A JP2019537883 A JP 2019537883A JP 7030820 B2 JP7030820 B2 JP 7030820B2
- Authority
- JP
- Japan
- Prior art keywords
- reactor
- ammonia
- concentration
- methane
- product gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C3/00—Cyanogen; Compounds thereof
- C01C3/02—Preparation, separation or purification of hydrogen cyanide
- C01C3/0208—Preparation in gaseous phase
- C01C3/0229—Preparation in gaseous phase from hydrocarbons and ammonia in the absence of oxygen, e.g. HMA-process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J12/00—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor
- B01J12/005—Chemical processes in general for reacting gaseous media with gaseous media; Apparatus specially adapted therefor carried out at high temperatures, e.g. by pyrolysis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/2425—Tubular reactors in parallel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00027—Process aspects
- B01J2219/00038—Processes in parallel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J2219/0873—Materials to be treated
- B01J2219/0881—Two or more materials
- B01J2219/0883—Gas-gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/24—Stationary reactors without moving elements inside
- B01J2219/2401—Reactors comprising multiple separate flow channels
- B01J2219/245—Plate-type reactors
- B01J2219/2469—Feeding means
- B01J2219/247—Feeding means for the reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
本発明は、生産ユニットをシアン化水素のための公称容量でより長い期間にわたり運転することを可能にする、アンモニアとメタンとを反応させることによるシアン化水素の製造方法に関する。 The present invention relates to a method for producing hydrogen cyanide by reacting ammonia with methane, which allows the production unit to operate at a nominal capacity for hydrogen cyanide for a longer period of time.
発明の背景
工業的規模でシアン化水素を製造するための、いわゆるBMAプロセス(メタンおよびアンモニアからの青酸(Blausaeure aus Methan und Ammoniak))においては、アンモニアおよびメタンを含む供給混合物を、白金を含む触媒上で吸熱反応において1000℃~1400℃の反応温度で反応させることで、シアン化水素および水素を含む生成物ガス混合物が得られる。BMAプロセスによりシアン化水素を製造するための工業用プラントにおいては、前記供給混合物は、白金触媒で内表面上が被覆された酸化アルミニウムの反応管中に導通され、これらの反応管は、ガス加熱式反応炉内に並列に配置されている。
Background of the Invention In the so - called BMA process for producing hydrogen cyanide on an industrial scale ( Blasauure aus Methane and Ammoniak ), a feed mixture containing ammonia and methane contains platinum. By reacting on a catalyst at a reaction temperature of 1000 ° C. to 1400 ° C. in a heat absorption reaction, a product gas mixture containing hydrogen cyanide and hydrogen is obtained. In an industrial plant for producing hydrogen cyanide by the BMA process, the feed mixture is conducted into a reaction tube of aluminum oxide whose inner surface is coated with a platinum catalyst, and these reaction tubes are gas-heated reactions. They are arranged in parallel in the furnace.
BMAプロセスで使用される高温では、前記供給混合物中に含まれるメタンおよびその他の炭化水素は、炭素および水素へと分解され得、そしてアンモニアは、窒素および水素へと分解され得る。したがって、BMAプロセスは、通常はモル過剰のアンモニアを使用して不完全なメタン転化で行われ、こうして未反応のアンモニアおよび未反応のメタンを含有する生成物ガス混合物が得られ、その際、アンモニア濃度は、メタン濃度よりも高い。前記供給混合物中での1.01:1~1.30:1の範囲内のアンモニア対炭素のモル比が文献で報告されている。F.Endter,Chemie-Ing.-Techn.30(1958)305-310は、供給混合物中での1.05:1のアンモニア対炭素のモル比での工業用プラントの運転により、71.8体積%の水素、22.9体積%のシアン化水素、2.5体積%のアンモニア、1.7体積%のメタン、および1.1体積%の窒素を含有する生成物ガス混合物が得られることを開示している。 At the high temperatures used in the BMA process, methane and other hydrocarbons contained in the feed mixture can be decomposed into carbon and hydrogen, and ammonia can be decomposed into nitrogen and hydrogen. Therefore, the BMA process is usually carried out with incomplete methane conversion using a molar excess of ammonia, thus resulting in a product gas mixture containing unreacted ammonia and unreacted methane, in which ammonia. The concentration is higher than the methane concentration. Ammonia to carbon molar ratios in the range 1.01: 1 to 1.30: 1 in the feed mixture have been reported in the literature. F. Ender, Chemie-Ing. -Techn. 30 (1958) 305-310 had 71.8% by volume hydrogen and 22.9% by volume of hydrogen cyanide by operating an industrial plant at a molar ratio of ammonia to carbon of 1.05: 1 in the feed mixture. , 2.5% by volume ammonia, 1.7% by volume of methane, and 1.1% by volume of nitrogen-containing product gas mixture is disclosed.
独国特許出願公開第2947498号明細書(DE2947498A1)は、BMAプロセスの生成物ガス混合物からの未反応のアンモニアを、ゼオライト上での吸収に続く脱着により回収することを開示している。22%~25%のHCN、2%~5%のNH3、70%~75%のH2、および微量の水、CH4、およびN2を含有する生成物ガス混合物が例として開示され、その際、BMAプロセスは、単独の反応管を収容する研究用炉内で実施されている。 German Patent Application Publication No. 2947498 (DE2947498A1) discloses that unreacted ammonia from the product gas mixture of the BMA process is recovered by desorption following absorption on zeolite. A product gas mixture containing 22% to 25% HCN, 2% to 5% NH 3 , 70% to 75% H 2 , and trace amounts of water, CH 4 , and N 2 is disclosed as an example. At that time, the BMA process is carried out in a research furnace containing a single reaction tube.
BMAプロセスの間のメタンおよびその他の炭化水素の分解は、反応管の内表面上に炭素堆積物の形成をもたらし、結果的に反応管の閉塞をもたらし得る。酸化アルミニウムは脆いので、酸化アルミニウム反応管は、運転の間に破損することもある。反応炉の運転は、反応管が閉塞または破損された場合に、反応管へのガス供給を遮断することにより継続され得る。しかしながら、シアン化水素の所望の生産速度の維持には、残りの反応管への供給速度を増大させ、反応温度を高めて、高められた供給速度で十分な転化を達成することが必要とされる。これは一定の限界までしか行うことができず、反応炉は、運転停止となった反応管の数が一定の限界を超えた場合に、閉塞または破損された反応管を取り替えるために操業停止にする必要がある。反応管を取り替えるために必要な反応炉の冷却、および反応温度への再加熱は、炉の材料に機械的応力をかけ、反応炉の操業時間を減らす。反応炉の運転停止はまた、シアン化水素生産プラントの出力を一時的に低下させる。したがって、できる限り長い期間にわたりBMAプロセスにおいて反応炉を運転することが求められている。 Decomposition of methane and other hydrocarbons during the BMA process can result in the formation of carbon deposits on the inner surface of the reaction tube, resulting in blockage of the reaction tube. Since aluminum oxide is brittle, aluminum oxide reaction tubes can also be damaged during operation. Operation of the reactor may be continued by shutting off the gas supply to the reaction tube if the reaction tube is blocked or damaged. However, maintaining the desired production rate of hydrogen cyanide requires increasing the rate of supply to the remaining reaction tubes, increasing the reaction temperature, and achieving sufficient conversion at the increased supply rate. This can only be done up to a certain limit, and the reactor will be shut down to replace the blocked or damaged reaction tube if the number of outaged reaction tubes exceeds a certain limit. There is a need to. The cooling of the reactor and the reheating to the reaction temperature required to replace the reactor tube puts mechanical stress on the reactor material and reduces the operating time of the reactor. Shutdown of the reactor also temporarily reduces the output of the hydrogen cyanide production plant. Therefore, it is required to operate the reactor in the BMA process for as long as possible.
独国特許出願公開第2421166号明細書(DE2421166)は、反応管に沿った圧力降下が25%~45%だけ増大した場合に、反応管中に二酸化炭素流を一時的に導通させることにより反応管内部に形成する炭素堆積物を定期的に除去することによって、BMAプロセスのためにより長い運転期間を達成することができることを教示している。独国特許出願公開第2421166号明細書(DE2421166)はさらに、3日~7日の間隔での追加のアンモニア処理を提案しており、その際、通常の運転で使用される1.05~1.075のアンモニア対炭素のモル比は、20分を超過することのない期間にわたり1.20~1.30へと一時的に上昇される。独国特許出願公開第2421166号明細書(DE2421166)はまた、種々の年数の反応管を収容する反応炉に関して、供給混合物中のアンモニア含量を、生成物ガス混合物中のメタン濃度よりも0.5体積%~1体積%高い生成物ガス混合物中のアンモニア濃度が得られるように調節するべきであると提案している。独国特許出願公開第2421166号明細書(DE2421166)は、この関連において、そのような僅かに高められたアンモニア含量は、触媒を損傷しないことを教示している。 German Patent Application Publication No. 242116 (DE242116) reacts by temporarily conducting a carbon dioxide stream through the reaction tube when the pressure drop along the reaction tube increases by 25% to 45%. It teaches that a longer operating period can be achieved for the BMA process by regularly removing the carbon deposits that form inside the pipe. German Patent Application Publication No. 242116 (DE242116) further proposes additional ammonia treatment at intervals of 3-7 days, 1.05-1 to which is used in normal operation. The molar ratio of ammonia to carbon of .075 is temporarily increased from 1.20 to 1.30 over a period not exceeding 20 minutes. German Patent Application Publication No. 242116 (DE242116) also sets the ammonia content in the feed mixture to 0.5 more than the methane concentration in the product gas mixture for reactors accommodating reaction tubes of various ages. It is suggested that the concentration of ammonia in the product gas mixture should be adjusted to be 100% to 1% by volume higher. German Patent Application Publication No. 242116 (DE242116) teaches in this regard that such slightly increased ammonia content does not damage the catalyst.
発明の概要
ここで、反応炉がBMAプロセスにおいて閉塞または破損された反応管を取り替えることが必要となるまで運転され得る期間は、生成物ガス混合物中のアンモニア濃度と生成物ガス混合物中のメタン濃度との間の濃度差を、その時間の大部分にわたり1体積%より高い値で維持して該プロセスを行うことによって、この濃度差を0.5体積%~1体積%の範囲で維持する先行技術の方法と比較してかなり延長され得ることが判明した。
Summary of the Invention Here, the ammonia concentration in the product gas mixture and the methane concentration in the product gas mixture are the periods during which the reactor can be operated until it becomes necessary to replace the blocked or damaged reaction tube in the BMA process. Preceding that this concentration difference is maintained in the range of 0.5% by volume to 1% by volume by performing the process while maintaining a concentration difference between and above 1% by volume for most of the time. It turns out that it can be significantly extended compared to the method of technology.
したがって、本発明の主題は、アンモニアおよびメタンを含む供給混合物を、白金を含む触媒で内表面上が被覆された反応管中に1000℃~1400℃の反応温度で導通させることを含み、こうしてシアン化水素、水素、未反応のアンモニア、および未反応のメタンを含む生成物ガス混合物が得られるシアン化水素の製造方法であって、前記生成物ガス混合物中のアンモニア濃度が前記生成物ガス混合物中のメタン濃度よりも高く、ここで、少なくとも100時間の期間にわたって、前記アンモニア濃度と前記メタン濃度との間の濃度差を、前記時間の少なくとも80%にわたり前記反応温度の調節、前記供給混合物中のアンモニア対炭素のモル比の調節、前記供給混合物の供給速度の調節、または前記調節の任意の組み合わせにより1.05体積%~3.0体積%の範囲内に維持する、方法である。 Accordingly, the subject of the present invention comprises conducting a feed mixture containing ammonia and methane into a reaction tube whose inner surface is coated with a catalyst containing platinum at a reaction temperature of 1000 ° C to 1400 ° C, thus hydrogen cyanide. A method for producing hydrogen cyanide, which provides a product gas mixture containing hydrogen, unreacted ammonia, and unreacted methane, wherein the ammonia concentration in the product gas mixture is higher than the methane concentration in the product gas mixture. Also high, here the concentration difference between the ammonia concentration and the methane concentration over a period of at least 100 hours, the adjustment of the reaction temperature over at least 80% of the time, the ammonia vs. carbon in the feed mixture. A method of maintaining in the range of 1.05% by volume to 3.0% by volume by adjusting the molar ratio, adjusting the supply rate of the feed mixture, or any combination of said adjustments.
発明の詳細な説明
シアン化水素の製造のための本発明の方法においては、アンモニアおよびメタンを含む供給混合物が、白金を含む触媒で内表面上が被覆された反応管中に導通される。アンモニアとメタンとの反応は、1000℃~1400℃の反応温度で実施され、こうしてシアン化水素、水素、未反応のアンモニア、および未反応のメタンを含む生成物ガス混合物が得られる。
Detailed Description of the Invention In the method of the invention for the production of hydrogen cyanide, a feed mixture containing ammonia and methane is conducted in a reaction tube whose inner surface is coated with a catalyst containing platinum. The reaction of ammonia with methane is carried out at a reaction temperature of 1000 ° C to 1400 ° C, thus resulting in a product gas mixture containing hydrogen cyanide, hydrogen, unreacted ammonia and unreacted methane.
前記供給混合物は、好ましくは主成分としてアンモニアおよびメタンを含み、さらにメタンに加えてエタンまたはプロパン等の炭化水素を含み得る。しかしながら、メタン以外の炭化水素の含量は、好ましくは低く保たれ、メタンは好ましくは、ガス状供給混合物中に含まれる炭化水素の少なくとも90体積%、より好ましくは少なくとも98体積%を成す。メタン以外の炭化水素の含量が低い供給混合物の使用は、より高級の炭化水素の熱分解により引き起こされる反応管中の炭素堆積物の形成を減らす。 The feed mixture preferably contains ammonia and methane as main components, and may further contain hydrocarbons such as ethane or propane in addition to methane. However, the content of hydrocarbons other than methane is preferably kept low, with methane preferably forming at least 90% by volume, more preferably at least 98% by volume of the hydrocarbons contained in the gaseous feed mixture. The use of feed mixtures with low content of hydrocarbons other than methane reduces the formation of carbon deposits in the reaction tube caused by the thermal decomposition of higher grade hydrocarbons.
前記供給混合物中のアンモニアおよびメタンの合計量は、好ましくは少なくとも90体積%、より好ましくは少なくとも98体積%である。前記供給混合物は、好ましくは低い含量の酸素を有し、好ましくは4体積%未満の酸素、より好ましくは1体積%未満の酸素を含む。前記供給混合物は、好ましくは天然ガスとガス状アンモニアとの混合により調製される。好ましくは、天然ガス供給網からの精製されて、そこから二酸化炭素および硫黄化合物が除去された天然ガスが使用される。前記供給混合物は、好ましくはメタンおよびその他の炭化水素に対して僅かにモル過剰のアンモニアを、1.01:1~1.30:1、好ましくは1.05:1~1.16:1のアンモニア対炭素のモル比で含む。モル過剰のアンモニアの使用は、メタンの高い転化率を可能にし、メタンの熱分解により引き起こされる反応管中の炭素堆積物の形成を減らす。 The total amount of ammonia and methane in the feed mixture is preferably at least 90% by volume, more preferably at least 98% by volume. The feed mixture preferably has a low content of oxygen, preferably less than 4% by volume, more preferably less than 1% by volume. The feed mixture is preferably prepared by mixing natural gas with gaseous ammonia. Preferably, natural gas is used that has been purified from the natural gas supply network from which carbon dioxide and sulfur compounds have been removed. The feed mixture preferably contains a slight molar excess of ammonia relative to methane and other hydrocarbons, 1.01: 1 to 1.30: 1, preferably 1.05: 1 to 1.16: 1. Included in the molar ratio of ammonia to carbon. The use of molar excess ammonia allows for high conversion of methane and reduces the formation of carbon deposits in the reaction tube caused by the thermal decomposition of methane.
アンモニアとメタンとの反応は、1000℃~1400℃の反応温度で白金金属を含む触媒の存在下で、内表面上に触媒で被覆された反応管中に供給混合物を導通させることにより行われる。メタンおよびアンモニアをシアン化水素および水素にする反応は、吸熱反応であり、必要とされる反応温度は、一般的に反応管の外部加熱により提供される。該反応は、好ましくは、並行して運転される10本~130本の反応管を好ましくは収容する反応炉内で行われ、該反応管は、好ましくは、天然ガスまたは天然ガスと水素との混合物を燃料として使用するガスバーナーからの燃焼ガスで加熱される。各々の反応炉は、好ましくは、供給混合物を炉の反応管に分配するための供給導管と、炉の反応管中で形成された生成物ガス混合物を回収する生成物導管とを有する。適切な反応炉は、先行技術、例えば独国特許出願公開第1041476号明細書(DE1041476)、欧州特許出願公開第0074504号明細書(EP0074504A1)、および欧州特許出願公開第0125395号明細書(EP0125395A2)から公知である。 The reaction between ammonia and methane is carried out by conducting a feed mixture in a reaction tube whose inner surface is coated with a catalyst in the presence of a catalyst containing platinum metal at a reaction temperature of 1000 ° C to 1400 ° C. The reaction of converting methane and ammonia to hydrogen cyanide and hydrogen is an endothermic reaction and the required reaction temperature is generally provided by external heating of the reaction tube. The reaction is preferably carried out in a reaction furnace preferably containing 10 to 130 reaction tubes operated in parallel, wherein the reaction tubes are preferably natural gas or natural gas and hydrogen. It is heated by combustion gas from a gas burner that uses the mixture as fuel. Each reactor preferably has a supply conduit for distributing the feed mixture to the reactor reaction tube and a product conduit for recovering the product gas mixture formed in the reactor reaction tube. Suitable reactors include prior art such as German Patent Application Publication No. 1041476 (DE1041476), European Patent Application Publication No. 0074504 (EP0074504A1), and European Patent Application Publication No. 0125395A2. Is known from.
前記反応管は、好ましくは、酸化アルミニウムまたは炭化ケイ素等の耐熱性セラミック材料でできており、好ましくは気密な焼結された酸化アルミニウムでできている。約2mの長さおよび約2cmの内径の適切な円筒の酸化アルミニウム管は市販されている。該反応管は、先行技術、例えば欧州特許出願公開第0299175号明細書(EP0299175A1)、欧州特許出願公開第0407809号明細書(EP0407809A1)、および欧州特許出願公開第0803470号明細書(EP0803470A1)から公知の方法を使用して白金触媒で被覆され得る。前記反応管は、供給混合物への熱伝達を改善するために、独国特許出願公開第1078554号明細書(DE1078554)、国際公開第2006/050781号(WO2006/050781A2)、および国際公開第2015/052066号(WO2015/052066A1)に記載される内部取付物、または国際公開第2014/198502号(WO2014/198502A1)に記載される内表面上のリブを備え得る。 The reaction tube is preferably made of a heat resistant ceramic material such as aluminum oxide or silicon carbide, and is preferably made of airtight sintered aluminum oxide. Suitable cylindrical aluminum oxide tubes with a length of about 2 m and an inner diameter of about 2 cm are commercially available. The reaction tube is known from the prior art, for example, European Patent Application Publication No. 0299175 (EP0299175A1), European Patent Application Publication No. 04077809 (EP0407809A1), and European Patent Application Publication No. 0803470 (EP0803470A1). Can be coated with a platinum catalyst using the method of. The reaction tube is used to improve heat transfer to the feed mixture in German Patent Application Publication No. 10785554 (DE10785554), International Publication No. 2006/050781 (WO2006 / 050781A2), and International Publication No. 2015 /. It may include internal attachments as described in 052066 (WO2015 / 052066A1) or ribs on the inner surface as described in WO 2014/198502 (WO2014 / 198502A1).
アンモニアとメタンとの反応により、シアン化水素、水素、未反応のアンモニア、および未反応のメタンを含む生成物ガス混合物が得られる。前記生成物ガス混合物中のアンモニア濃度は、一般的に前記メタン濃度よりも高く、メタン濃度より高いアンモニア濃度は、供給混合物中のアンモニア対炭素のモル比を前記の1.01:1~1.30:1の範囲内に調節することにより簡単に達成することができる。該生成物ガス混合物は、アンモニアの窒素および水素への分解により形成される窒素も含有し得る。 The reaction of ammonia with methane gives a product gas mixture containing hydrogen cyanide, hydrogen, unreacted ammonia, and unreacted methane. The ammonia concentration in the product gas mixture is generally higher than the methane concentration, and the ammonia concentration higher than the methane concentration makes the molar ratio of ammonia to carbon in the feed mixture 1.01: 1 to 1. It can be easily achieved by adjusting within the range of 30: 1. The product gas mixture may also contain nitrogen formed by the decomposition of ammonia into nitrogen and hydrogen.
本発明の方法は、シアン化水素を公称容量で製造する場合に、できる限り長くシアン化水素を製造するために使用される反応管を運転することを目的とする。これは、反応条件を調節することで、生成物ガス混合物中のメタン濃度より1.05体積%~3.0体積%高い生成物ガス混合物中のアンモニア濃度を、前記時間の少なくとも80%にわたり維持することにより達成される。該アンモニア濃度と該メタン濃度との間の濃度差は、好ましくは1.1体積%~2.5体積%である。該アンモニア濃度と該メタン濃度との間の濃度差は、反応温度の調節、前記供給混合物中のアンモニア対炭素のモル比の調節、前記供給混合物の供給速度の調節、またはこれらの措置の任意の組み合わせにより前記範囲内に維持され得る。反応温度の増大は、前記濃度差に減少をもたらし、反応温度の低下は、前記濃度差に増大をもたらすこととなる。供給混合物中のアンモニア対炭素のモル比の増大は、前記濃度差に増大をもたらし、供給混合物中のアンモニア対炭素のモル比の減少は、前記濃度差に減少をもたらすこととなる。供給混合物の供給速度の増大は、前記濃度差に増大をもたらし、供給混合物の供給速度の減少は、前記濃度差に減少をもたらすこととなる。好ましくは、供給混合物中のアンモニア対炭素のモル比は一定に保たれ、前記濃度差は、反応温度の調節により維持される。反応温度、供給混合物中のアンモニア対炭素のモル比、および供給混合物の供給速度が一定に保たれる場合に、生成物ガス混合物中のアンモニア濃度とメタン濃度との間の濃度差は、時間の経過と共に触媒劣化の結果として変化することとなる。したがって、一定の濃度差の維持は、一般的に時間の経過と共に作業条件を調節することを必要とする。 The method of the present invention is intended to operate the reaction tube used to produce hydrogen cyanide for as long as possible when producing hydrogen cyanide in nominal capacity. This maintains the ammonia concentration in the product gas mixture 1.05% by volume to 3.0% by volume higher than the methane concentration in the product gas mixture over at least 80% of the time by adjusting the reaction conditions. Achieved by doing. The concentration difference between the ammonia concentration and the methane concentration is preferably 1.1% by volume to 2.5% by volume. The concentration difference between the ammonia concentration and the methane concentration can be an adjustment of the reaction temperature, an adjustment of the molar ratio of ammonia to carbon in the feed mixture, an adjustment of the feed rate of the feed mixture, or any of these measures. Depending on the combination, it can be maintained within the above range. An increase in the reaction temperature causes a decrease in the concentration difference, and a decrease in the reaction temperature causes an increase in the concentration difference. An increase in the molar ratio of ammonia to carbon in the feed mixture will result in an increase in the concentration difference, and a decrease in the molar ratio of ammonia to carbon in the feed mixture will result in a decrease in the concentration difference. An increase in the supply rate of the feed mixture will result in an increase in the concentration difference, and a decrease in the supply rate of the supply mixture will result in a decrease in the concentration difference. Preferably, the molar ratio of ammonia to carbon in the feed mixture is kept constant and the concentration difference is maintained by adjusting the reaction temperature. When the reaction temperature, the molar ratio of ammonia to carbon in the feed mixture, and the feed rate of the feed mixture are kept constant, the concentration difference between the ammonia concentration and the methane concentration in the product gas mixture is of time. It will change over time as a result of catalyst deterioration. Therefore, maintaining a constant concentration difference generally requires adjusting the working conditions over time.
運転条件は、一般的に、供給混合物中に含まれるメタンおよびその他の炭化水素の高い転化率が得られるように、好ましくは4体積%未満の生成物ガス混合物中のメタン濃度が得られるように調節される。 The operating conditions are generally such that high conversions of methane and other hydrocarbons contained in the feed mixture are obtained, preferably less than 4% by volume of methane concentration in the product gas mixture. Be adjusted.
特許請求の範囲に記載の方法の利点は、前記アンモニア濃度と前記メタン濃度との間の濃度差を、少なくとも100時間の十分に長い期間にわたり1.05体積%~3.0体積%の範囲内に維持することにより達成される。その期間は、100時間~100000時間、好ましくは4000時間~40000時間であり得る。その期間には、好ましくは、一般的に15時間~60時間かかる反応管の最初の始動時の触媒のコンディショニング段階を除く反応炉の全運転時間が含まれる。前記濃度差は、全期間を通じて1.05体積%~3.0体積%の範囲内である必要はないが、その期間の20%以下にわたってはより低くてよい。前記濃度差は、どのような延長された期間にわたっても3.0体積%よりは高くするべきではない。好ましくは、少なくとも100時間の期間の間、前記濃度差は、その時間の少なくとも95%、好ましくはその時間の少なくとも98%にわたり3.0体積%以下である。 The advantage of the method described in the claims is that the concentration difference between the ammonia concentration and the methane concentration is in the range of 1.05% by volume to 3.0% by volume over a sufficiently long period of at least 100 hours. Achieved by maintaining in. The period can be 100 to 100,000 hours, preferably 4000 to 40,000 hours. The period preferably includes the total operating time of the reactor, excluding the catalyst conditioning step at the first start of the reaction tube, which typically takes 15-60 hours. The concentration difference need not be in the range of 1.05% by volume to 3.0% by volume over the entire period, but may be lower over 20% or less of that period. The concentration difference should not be higher than 3.0% by volume over any extended period. Preferably, for a period of at least 100 hours, the concentration difference is 3.0% by volume or less over at least 95% of that time, preferably at least 98% of that time.
高められた濃度差は、例えば独国特許出願公開第2421166号明細書(DE2421166A1)の第4頁第25行~36行に記載される反応管中のスート堆積物を防止するための方法の実施のためには短い期間の間は許容され得る。この目的のために、供給混合物中のアンモニア対炭素のモル比を、15時間~300時間の時間間隔で30分以下の期間にわたり10%~30%だけ増大させることが好ましい。 The increased concentration difference is, for example, the implementation of the method for preventing soot deposits in the reaction tube described in page 4, lines 25-36 of German Patent Application Publication No. 242166 (DE242116A1). May be acceptable for a short period of time. For this purpose, it is preferred to increase the molar ratio of ammonia to carbon in the feed mixture by 10% to 30% over a period of 30 minutes or less at time intervals of 15 to 300 hours.
好ましい実施形態においては、前記濃度差は、前記時間の少なくとも95%にわたり1.1体積%~2.1体積%の範囲内の一定値で維持される。前記時間の少なくとも95%にわたりこの狭い範囲内の一定の濃度差に保つことは、反応管の閉塞または破損を防ぐのに特に効果的である。 In a preferred embodiment, the concentration difference is maintained at a constant value in the range of 1.1% by volume to 2.1% by volume over at least 95% of the time. Keeping a constant concentration difference within this narrow range over at least 95% of the time is particularly effective in preventing blockage or breakage of the reaction tube.
1.1体積%未満の濃度差で運転される先行技術の方法と比較して、本発明の方法は、反応炉のより長い運転時間を可能にするだけでなく、より低い反応温度でシアン化水素についての同じ出力速度も達成可能であり、それにより反応炉の寿命は高まり、反応管の加熱の間に生ずる熱損失は減少し、こうして該方法のエネルギー消費量は低減される。 1.1 Compared to prior art methods operated with concentration differences of less than% by volume, the methods of the invention not only allow longer operating times of the reactor, but also for hydrogen cyanide at lower reaction temperatures. The same output rate is also achievable, thereby increasing the life of the reactor and reducing the heat loss that occurs during heating of the reaction vessel, thus reducing the energy consumption of the method.
本発明の方法は、一定のシアン化水素生産速度で並行して運転され、反応管の閉塞または破損により引き起こされる生産能力の損失が残りの反応管への供給速度を増大させることにより補償される多数の反応管を用いてシアン化水素を製造するために特に有利である。運転時間にわたる個々の反応管への供給速度のそのような増大は、シアン化水素の収率の減少をもたらすこととなる。したがって、供給されたアンモニアに対して計算されたシアン化水素の収率は、本発明の方法の場合に1.1体積%未満の濃度差で運転された先行技術の方法と比較して、最初は僅かにより低いものの、全運転時間にわたるアンモニアに対する平均収率は、本発明の方法の場合にはより高く、そのことは未転化のアンモニアのより高い濃度で運転される方法にとっては驚くべきことである。 The method of the present invention is operated in parallel at a constant hydrogen cyanide production rate, and the loss of production capacity caused by blockage or breakage of the reaction tube is compensated by increasing the supply rate to the remaining reaction tubes. It is particularly advantageous for producing hydrogen cyanide using a reaction tube. Such an increase in the rate of supply to the individual reaction tubes over operating hours will result in a decrease in the yield of hydrogen cyanide. Therefore, the calculated yield of hydrogen cyanide for the supplied ammonia is initially small compared to the prior art method operated with a concentration difference of less than 1.1% by volume in the case of the method of the invention. Although lower, the average yield to ammonia over the entire operating time is higher for the method of the invention, which is surprising for methods operated at higher concentrations of unconverted ammonia.
生成物ガス混合物中のアンモニアおよびメタンの濃度は、ガス分析のために慣用の方法により測定され得る。例えば、アンモニアの濃度は、アンモニアを既知の量の酸を含有する溶液中に吸収させ、消費されなかった酸を滴定することにより測定され得る。メタンは、生成物ガスからのアンモニアおよびシアン化水素を酸性水溶液およびアルカリ性水溶液で吸収させた後にGC分析により測定され得る。好ましくは、生成物ガス混合物中のアンモニアおよびメタンの濃度は、赤外分光分析またはガスクロマトグラフィーにより同時に測定される。生成物ガス混合物の赤外分析は、1718cm-1でのアンモニアの赤外吸収および2940cm-1でのメタンの赤外吸収と、既知の組成物の混合物での較正に基づき実施され得る。赤外分析は、好ましくはFT-IR分光器を用いて行われる。生成物ガス混合物のGC分析は、好ましくはメタン分析およびアンモニア分析のために異なるカラムを用いてサンプルスプリッターを使用して実施される。メタンは、好ましくはモレキュラーシーブ充填カラムで分析され、アンモニアは、好ましくはキャピラリーカラム、例えばAgilent J&W社製のPoraPLOT Qカラムにより分析される。 The concentrations of ammonia and methane in the product gas mixture can be measured by conventional methods for gas analysis. For example, the concentration of ammonia can be measured by absorbing ammonia in a solution containing a known amount of acid and titrating the unconsumed acid. Methane can be measured by GC analysis after absorption of ammonia and hydrogen cyanide from the product gas in acidic and alkaline aqueous solutions. Preferably, the concentrations of ammonia and methane in the product gas mixture are measured simultaneously by infrared spectroscopy or gas chromatography. Infrared analysis of the product gas mixture can be performed on the basis of infrared absorption of ammonia at 1718 cm -1 and infrared absorption of methane at 2940 cm -1 and calibration with a mixture of known compositions. Infrared analysis is preferably performed using an FT-IR spectroscope. GC analysis of the product gas mixture is preferably performed using a sample splitter with different columns for methane and ammonia analysis. Methane is preferably analyzed on a molecular sieve-filled column and ammonia is preferably analyzed on a capillary column, eg, a PoraPLOT Q column manufactured by Agilent J & W.
本発明の方法は、好ましくは、1基以上の反応器を備えて、それぞれの反応器が並行して運転される少なくとも2基の反応炉を備えるプラント中で実施される。それぞれの反応炉は、並行して運転される10本~130本の反応管を含む。好ましくは、さらに先に記載された反応炉が使用される。該プラントのそれぞれの反応器は、該反応器の反応炉の生成物ガス混合物を回収する反応器生成物導管を備える。該プラントは、好ましくは1基~30基の反応器、より好ましくは2基~15基の反応器を備え、その際、それぞれの反応器は、2基~20基の反応炉、好ましくは8基~16基の反応炉を備える。 The method of the present invention is preferably carried out in a plant equipped with one or more reactors and at least two reactors in which each reactor is operated in parallel. Each reactor contains 10 to 130 reaction tubes operated in parallel. Preferably, the reactor described further above is used. Each reactor in the plant comprises a reactor product conduit for recovering the product gas mixture of the reactor in the reactor. The plant preferably comprises 1 to 30 reactors, more preferably 2 to 15 reactors, wherein each reactor has 2 to 20 reactors, preferably 8 reactors. It is equipped with 16 to 16 reactors.
アンモニア濃度およびメタン濃度は、単独の反応炉からの合された生成物ガス混合物、反応器生成物導管中の合された生成物ガス混合物、または両方の生成物ガス混合物において分析され、こうして反応炉または全反応器についての濃度差が測定され得る。好ましくは、生成物ガス混合物中のアンモニアおよびメタンの濃度は、赤外分光分析またはガスクロマトグラフィーにより同時に測定される。 Ammonia and methane concentrations are analyzed in the combined product gas mixture from a single reactor, the combined product gas mixture in the reactor product conduit, or both product gas mixtures, and thus the reactor. Alternatively, the concentration difference for all reactors can be measured. Preferably, the concentrations of ammonia and methane in the product gas mixture are measured simultaneously by infrared spectroscopy or gas chromatography.
好ましくは、前記運転条件は、プラントのそれぞれの反応炉について、前記反応炉からの合された生成物ガス混合物中の濃度差が、1.05体積%~3.0体積%の範囲内で維持されるように調節される。すなわち、それぞれの反応炉について、該濃度差は、反応炉からの合された生成物ガス混合物中で維持される。反応器の複数の反応炉は、前記範囲内の種々の濃度差で運転され得る。同様に、該プラントの反応器は、前記範囲内の種々の濃度差で運転され得る。好ましくは、プラントのそれぞれの反応器は、同じ濃度差で運転され、より好ましくはそれぞれの反応炉は、同じ濃度差で運転される。 Preferably, the operating conditions are such that for each reactor in the plant, the concentration difference in the combined product gas mixture from the reactor is maintained within the range of 1.05% by volume to 3.0% by volume. It is adjusted to be. That is, for each reactor, the concentration difference is maintained in the combined product gas mixture from the reactor. Multiple reactors of the reactor may be operated with different concentration differences within the above range. Similarly, the reactor of the plant can be operated with various concentration differences within the above range. Preferably, each reactor in the plant is operated with the same concentration difference, more preferably each reactor is operated with the same concentration difference.
反応管が閉塞または破損した場合には、この反応管への供給混合物の供給は、好ましくは停止され、こうして閉塞または破損された反応管を収容する反応炉を残りの反応管によりさらに運転することが可能となる。閉塞または破損された反応管を収容する反応炉に供給混合物を供給する速度は、シアン化水素についての一定の生産速度が維持されるように増大され得る。好ましくは、閉塞または破損された反応管を含む反応器に供給混合物を供給する速度は、本質的に一定に保たれ、それは、閉塞または破損された反応管への供給が同じ反応炉のその他の反応管に転送されるだけでなく、該反応器のその他の反応炉へも転送されるという効果を有する。好ましくは、閉塞または破損された反応管の供給物が転送される先の1基以上の反応炉の反応温度は、反応炉または反応器について一定の濃度差が維持されるように増大される。 If the reaction tube is blocked or damaged, the supply of the feed mixture to this reaction tube is preferably stopped and the reactor containing the thus blocked or damaged reaction tube is further operated by the remaining reaction tubes. Is possible. The rate at which the feed mixture is supplied to the reactor containing the blocked or damaged reaction tube can be increased to maintain a constant production rate for hydrogen cyanide. Preferably, the rate at which the feed mixture is fed to the reactor, including the closed or broken reactor, is kept essentially constant, which is the other of the reactor with the same feed to the closed or broken reactor. It has the effect of not only being transferred to the reaction tube, but also to other reactors of the reactor. Preferably, the reaction temperature of one or more reactors to which the blockaged or damaged reactor tube feed is transferred is increased so that a constant concentration difference is maintained for the reactor or reactor.
炭素堆積物による反応管の閉塞を防ぐために、反応炉の1本以上の反応管は、該炉の1本以上の反応管を通して二酸化炭素を導通させつつ、さらに該炉を加熱することにより、好ましくは独国特許出願公開第2421166号明細書(DE2421166A1)に記載される方法を適用することにより炭素堆積物を除去するために一時的に運転停止にすることができる。 In order to prevent blockage of the reaction tube by carbon deposits, it is preferable that one or more reaction tubes of the reactor are further heated while conducting carbon dioxide through one or more reaction tubes of the reactor. Can be temporarily shut down to remove carbon deposits by applying the method described in Japanese Patent Application Publication No. 242166 (DE242116A1).
実施例
例1(比較例)
長さ2100mmおよび内径17mmの焼結された酸化アルミニウムから構成される円筒形反応管を、白金含有触媒で被覆し、欧州特許出願公開第0407809号明細書(EP0407809A)の実施例6に記載されるように活性化させた。アンモニア対炭素のモル比1.10を有する28.0mol/hのアンモニアおよび25.5mol/hのメタンから構成される供給ガス流を、次いで、研究用炉内で1240℃に加熱された鉛直方向を向いた反応管中に下方から導通させた。該反応管から出てくる生成物ガス混合物を分析した。シアン化水素の収率は、アンモニアを基準に87.8%であり、メタンを基準に96.6%であった。
Example 1 (Comparative Example)
A cylindrical reaction tube composed of sintered aluminum oxide having a length of 2100 mm and an inner diameter of 17 mm is coated with a platinum-containing catalyst and is described in Example 6 of Japanese Patent Application Publication No. 0407789 (EP04078709A). Was activated. A stream of feed gas composed of 28.0 mol / h ammonia with a molar ratio of ammonia to carbon of 1.10 and 25.5 mol / h methane was then heated vertically in a research furnace to 1240 ° C. It was conducted from below in the reaction tube facing. The product gas mixture coming out of the reaction tube was analyzed. The yield of hydrogen cyanide was 87.8% based on ammonia and 96.6% based on methane.
例2
例1の場合と同じアンモニア対炭素のモル比1.10を有する36.0mol/hのアンモニアおよび32.7mol/hのメタンから構成される供給ガス流を用いて、例1を繰り返した。シアン化水素の収率は、アンモニアを基準に83.8%であり、メタンを基準に92.1%であった。
Example 2
Example 1 was repeated using a feed gas stream composed of 36.0 mol / h ammonia and 32.7 mol / h methane having the same ammonia to carbon molar ratio of 1.10 as in Example 1. The yield of hydrogen cyanide was 83.8% based on ammonia and 92.1% based on methane.
例3
例1と同様に準備された反応管であって、生成物ガス混合物中のアンモニア濃度とメタン濃度との間の濃度差が1体積%未満である運転条件でシアン化水素を製造するための先行する実験で150時間超にわたり使用された反応管を使用した。アンモニア対炭素のモル比1.14を有する28.0mol/hのアンモニアおよび24.6mol/hのメタンから構成される供給ガス流を、次いで、研究用炉内で1330℃に加熱された鉛直方向を向いた反応管中に下方から導通させた。該反応管から出てくる生成物ガス混合物を定常状態に達した後に分析した。次いで、研究用炉の温度を、30℃のステップで1180℃に低下させ、毎回定常状態に達するまで待ってから生成物ガス混合物を分析した。第1表は、生成物ガス混合物中のアンモニアおよびメタンの濃度、濃度差、アンモニア基準およびメタン基準のシアン化水素の収率、ならびに生成されたシアン化水素の量および研究用炉の加熱のために燃焼されたガスの量から計算されるエネルギー消費量を示す。
Example 3
A prior experiment for producing hydrogen cyanide in a reaction tube prepared as in Example 1 under operating conditions where the concentration difference between the ammonia concentration and the methane concentration in the product gas mixture is less than 1% by volume. A reaction tube that had been used for over 150 hours was used. A stream of feed gas composed of 28.0 mol / h ammonia with a molar ratio of ammonia to carbon of 1.14 and 24.6 mol / h methane was then heated vertically in a research furnace to 1330 ° C. It was conducted from below in the reaction tube facing. The product gas mixture coming out of the reaction tube was analyzed after reaching steady state. The temperature of the research furnace was then lowered to 1180 ° C. in steps of 30 ° C. and waited until steady state was reached each time before analysis of the product gas mixture. Table 1 was burned for the concentrations of ammonia and methane in the product gas mixture, the concentration differences, the yields of ammonia-based and methane-based hydrogen cyanide, and the amount of hydrogen cyanide produced and the heating of the research furnace. Shows the energy consumption calculated from the amount of gas.
第1表
例4(比較例)
欧州特許出願公開第0125395号明細書(EP0125395A2)に記載されるデザインの10基の反応炉を備え、それぞれの反応炉が26本の反応管を収容する生産プラントの反応器を、アンモニア対炭素のモル比1.09を有するメタンおよびアンモニアの供給混合物を用いて運転した。供給物流を、約179kg/hのシアン化水素出力が維持されるように調節し、反応炉温度を、生成物ガス混合物中のアンモニア濃度とメタン濃度との間の濃度差が約0.5体積%に維持されるように調節した。アンモニアおよびメタンの濃度を、反応器生成物導管中で赤外分光分析およびGC分析により測定した。反応管中での炭素堆積物の形成を防ぐために、供給混合物中のアンモニア対炭素のモル比を、2日の間隔で15分間の期間にわたり20%だけ一時的に増大させた。さらなる措置として、二酸化炭素を、独国特許出願公開第2421166号明細書(DE2421166A1)に記載される手順に従い、約28日間の間隔で反応管中に導通させた。第2表は、HCN収率、閉塞または破損した反応管の数、使用される反応管当たりの平均負荷量、および19200時間の実行時間にわたる平均反応炉温度を示す。
Example 4 (comparative example)
Ammonia vs. carbon reactors in a production plant equipped with 10 reactors of the design described in European Patent Application Publication No. 0125395 (EP0125395A2), each containing 26 reaction tubes. It was operated with a feed mixture of methane and ammonia having a molar ratio of 1.09. The feed stream was adjusted to maintain a hydrogen cyanide output of about 179 kg / h and the reactor temperature was adjusted so that the concentration difference between the ammonia concentration and the methane concentration in the product gas mixture was about 0.5% by volume. Adjusted to be maintained. Concentrations of ammonia and methane were measured by infrared spectroscopic analysis and GC analysis in the reactor product conduit. To prevent the formation of carbon deposits in the reaction tube, the molar ratio of ammonia to carbon in the feed mixture was temporarily increased by 20% over a 15 minute period at 2-day intervals. As a further measure, carbon dioxide was conducted in the reaction tube at intervals of approximately 28 days according to the procedure described in German Patent Application Publication No. 242166 (DE242116A1). Table 2 shows the HCN yield, the number of blocked or damaged reactor tubes, the average load per reactor tube used, and the average reactor temperature over a run time of 19200 hours.
第2表
例5
例4を、アンモニア対炭素のモル比1.10を有する天然ガスおよびアンモニアの供給混合物を用いて繰り返し、反応炉温度を、生成物ガス混合物中のアンモニア濃度とメタン濃度との間の濃度差が約1.3体積%に維持されるように調節した。反応管中での炭素堆積物の形成は、例4よりもゆっくりと生じたので、供給混合物中のアンモニア対炭素のモル比を、5日間の間隔で一時的に増大させ、そして二酸化炭素を約3ヶ月~4ヶ月の間隔で反応管中に導通させた。第3表は、結果を示す。
Example 5
Example 4 is repeated using a natural gas with a molar ratio of ammonia to carbon of 1.10 and a feed mixture of ammonia, and the reactor temperature is determined by the concentration difference between the ammonia concentration and the methane concentration in the product gas mixture. It was adjusted to be maintained at about 1.3% by volume. The formation of carbon deposits in the reaction tube occurred more slowly than in Example 4, so the molar ratio of ammonia to carbon in the feed mixture was temporarily increased at 5-day intervals and carbon dioxide was reduced. Conduction was carried out in the reaction tube at intervals of 3 to 4 months. Table 3 shows the results.
第3表
Claims (16)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP16191019.5A EP3301075A1 (en) | 2016-09-28 | 2016-09-28 | Method for producing hydrogen cyanide |
EP16191019.5 | 2016-09-28 | ||
PCT/EP2017/074381 WO2018060196A1 (en) | 2016-09-28 | 2017-09-26 | Method for producing hydrogen cyanide |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2019529330A JP2019529330A (en) | 2019-10-17 |
JP7030820B2 true JP7030820B2 (en) | 2022-03-07 |
Family
ID=57042670
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2019537883A Active JP7030820B2 (en) | 2016-09-28 | 2017-09-26 | Method for producing hydrogen cyanide |
Country Status (6)
Country | Link |
---|---|
US (1) | US11897781B2 (en) |
EP (2) | EP3301075A1 (en) |
JP (1) | JP7030820B2 (en) |
CN (1) | CN109982970B (en) |
MY (1) | MY193998A (en) |
WO (1) | WO2018060196A1 (en) |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3055056B1 (en) | 2013-10-11 | 2019-12-18 | Evonik Operations GmbH | Reaction tube and method for the production of hydrogen cyanide |
EP3301075A1 (en) | 2016-09-28 | 2018-04-04 | Evonik Degussa GmbH | Method for producing hydrogen cyanide |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016526523A (en) | 2013-06-11 | 2016-09-05 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | Reaction tube and method for producing hydrogen cyanide |
US20160263558A1 (en) | 2013-10-11 | 2016-09-15 | Evonik Degussa Gmbh | Reaction tube and method for producing hydrogen cyanide |
Family Cites Families (42)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB191400461A (en) * | 1914-01-07 | 1915-07-15 | Max Mannesmann | Improvements in Packings for Shafts and Wheel Bearings. |
BE524838A (en) * | 1952-12-06 | |||
NL202236A (en) | 1954-09-18 | 1900-01-01 | ||
BE544845A (en) | 1955-02-03 | |||
GB969796A (en) | 1961-03-01 | 1964-09-16 | Exxon Research Engineering Co | Apparatus for heating fluids and tubes for disposal therein |
US3156544A (en) | 1962-10-01 | 1964-11-10 | Allied Chem | Apparatus for making combustible gas |
DE2421166C2 (en) | 1974-05-02 | 1984-12-20 | Degussa Ag, 6000 Frankfurt | Process for extending the life of platinum contact tubes in the production of hydrogen cyanide |
US3970435A (en) | 1975-03-27 | 1976-07-20 | Midland-Ross Corporation | Apparatus and method for methanation |
JPS5330491A (en) | 1976-09-02 | 1978-03-22 | Nippon Steel Corp | Massive catalyst body |
DE2811115A1 (en) | 1978-03-15 | 1979-09-27 | Hoechst Ag | CARRIER CATALYST FOR THE PRODUCTION OF VINYL ACETATE FROM ETHYLENE, ACETIC ACID AND OXYGEN IN THE GAS PHASE |
DE2913925C2 (en) | 1979-04-06 | 1982-06-03 | Degussa Ag, 6000 Frankfurt | Process for the production of hydrogen cyanide |
DE2923596A1 (en) | 1979-06-11 | 1980-12-18 | Selas Kirchner Gmbh | Hydrocarbon cracking or reforming furnace - with internally subdivided ceramic tubes for gas mixt. |
DE2936844A1 (en) | 1979-09-12 | 1981-04-02 | Degussa Ag, 6000 Frankfurt | METHOD FOR PRODUCING CYAN HYDROGEN |
DE2947498C2 (en) | 1979-11-24 | 1982-01-21 | Degussa Ag, 6000 Frankfurt | Process for the production of hydrogen cyanide |
DE3134851C2 (en) | 1981-09-03 | 1983-10-13 | Degussa Ag, 6000 Frankfurt | Tube furnace for carrying out gas reactions |
DE3309394C2 (en) | 1983-03-16 | 1985-11-14 | Degussa Ag, 6000 Frankfurt | Device for the production of hydrogen cyanide |
JPS59222428A (en) | 1983-05-31 | 1984-12-14 | Kobe Steel Ltd | Apparatus for highly efficient methanation |
ATE41202T1 (en) | 1985-01-16 | 1989-03-15 | Hamon Sobelco Sa | METHOD AND DEVICE FOR RECOVERING ENERGY FROM THE EXHAUST GAS OF A THERMAL POWER PLANT. |
DE3723535A1 (en) | 1987-07-16 | 1989-01-26 | Degussa | METHOD FOR PRODUCING CYAN HYDROGEN |
DE3915428A1 (en) | 1989-05-11 | 1990-11-15 | Hoechst Ceram Tec Ag | ALUMINUM OXIDE TUBES AND METHOD FOR THEIR PRODUCTION |
DE3923034A1 (en) | 1989-07-13 | 1991-02-07 | Degussa | METHOD FOR PRODUCING CATALYTICALLY EFFECTIVE COATINGS FOR THE PRODUCTION OF CYAN HYDROGEN |
DE3935073A1 (en) | 1989-10-20 | 1991-04-25 | Sued Chemie Ag | METHOD FOR THE CATALYTIC DEHYDRATION OF HYDROCARBONS, ESPECIALLY ALKYLAROMATES |
DE4128201A1 (en) | 1991-08-26 | 1993-03-04 | Hoechst Ceram Tec Ag | Sintered alumina reaction tube - contg. spiral insert, esp. for high temp. hydrogen cyanide synthesis |
DE19524158A1 (en) | 1995-07-03 | 1997-01-09 | Degussa | Process for the production of hydrocyanic acid |
DE19617040C1 (en) | 1996-04-27 | 1997-10-30 | Degussa | Process for the production of catalytically active coatings for the synthesis of hydrogen cyanide |
DE19653991A1 (en) | 1996-12-21 | 1998-06-25 | Degussa | Reactor for carrying out endothermic catalytic reactions |
US6221327B1 (en) * | 1998-05-15 | 2001-04-24 | Rohm And Haas Company | Catalyst system using flow-through radiation shielding and a process for producing hydrogen cyanide using the same |
US20020085967A1 (en) | 2000-12-18 | 2002-07-04 | Kabushiki Kaisha Toyota Chuo Kenkyusho | Process for generating hydrogen and apparatus for generating hydrogen |
US7070743B2 (en) | 2002-03-14 | 2006-07-04 | Invista North America S.A R.L. | Induction-heated reactors for gas phase catalyzed reactions |
US20050131263A1 (en) | 2002-07-25 | 2005-06-16 | Schmidt + Clemens Gmbh + Co. Kg, | Process and finned tube for the thermal cracking of hydrocarbons |
DE10309209A1 (en) | 2003-02-28 | 2004-09-09 | Degussa Ag | Process for the production of hydrogen cyanide by the BMA process and catalyst for its implementation |
WO2005085127A1 (en) | 2004-03-09 | 2005-09-15 | Nippon Oil Corporation | Method for producing hydrogen and system therefor |
US7309480B2 (en) | 2004-04-16 | 2007-12-18 | H2Gen Innovations, Inc. | Catalyst for hydrogen generation through steam reforming of hydrocarbons |
DE202004016252U1 (en) | 2004-08-12 | 2005-12-22 | Schmidt + Clemens Gmbh & Co. Kg | Composite pipe, for use in steam cracking of hydrocarbons or in rotary furnaces or refuse incinerators, comprises outer spun pipe and coaxial inner pipe which is made by compressing powder |
DE102004054727A1 (en) | 2004-11-12 | 2006-05-24 | Degussa Ag | Process for the preparation of hydrogen cyanide and reaction tube for the process |
PL2037202T3 (en) | 2006-07-05 | 2019-03-29 | Nippon Steel & Sumitomo Metal Corporation | Metal tube for thermal cracking reaction |
WO2009075692A2 (en) | 2007-05-14 | 2009-06-18 | Invista Technologies S.A.R.L. | High efficiency reactor and process |
AU2008323197A1 (en) | 2007-11-13 | 2009-05-22 | Basf Se | Improved method for producing hydrocyanic acid by catalytic dehydration of gaseous formamide |
EP2671636A1 (en) | 2012-06-06 | 2013-12-11 | Ammonia Casale S.A. | Pressure vessel with replaceable tubes |
CN105396589B (en) * | 2015-10-21 | 2018-01-16 | 大连理工大学 | A kind of metal load type catalyst and the method for synthesizing HCN |
EP3301075A1 (en) | 2016-09-28 | 2018-04-04 | Evonik Degussa GmbH | Method for producing hydrogen cyanide |
EP3339289A1 (en) | 2016-12-21 | 2018-06-27 | Evonik Degussa GmbH | Process for the preparation of methionine |
-
2016
- 2016-09-28 EP EP16191019.5A patent/EP3301075A1/en not_active Withdrawn
-
2017
- 2017-09-26 MY MYPI2019001695A patent/MY193998A/en unknown
- 2017-09-26 US US16/337,156 patent/US11897781B2/en active Active
- 2017-09-26 EP EP17778245.5A patent/EP3519359B1/en active Active
- 2017-09-26 WO PCT/EP2017/074381 patent/WO2018060196A1/en unknown
- 2017-09-26 CN CN201780072753.5A patent/CN109982970B/en active Active
- 2017-09-26 JP JP2019537883A patent/JP7030820B2/en active Active
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2016526523A (en) | 2013-06-11 | 2016-09-05 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | Reaction tube and method for producing hydrogen cyanide |
US20160263558A1 (en) | 2013-10-11 | 2016-09-15 | Evonik Degussa Gmbh | Reaction tube and method for producing hydrogen cyanide |
Also Published As
Publication number | Publication date |
---|---|
US11897781B2 (en) | 2024-02-13 |
WO2018060196A1 (en) | 2018-04-05 |
MY193998A (en) | 2022-11-07 |
CN109982970B (en) | 2020-08-04 |
EP3519359A1 (en) | 2019-08-07 |
JP2019529330A (en) | 2019-10-17 |
CN109982970A (en) | 2019-07-05 |
EP3301075A1 (en) | 2018-04-04 |
EP3519359B1 (en) | 2020-08-05 |
US20190225501A1 (en) | 2019-07-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
TWI812634B (en) | Autothermal ammonia cracking process | |
US8021448B2 (en) | Method and system for producing a hydrogen enriched fuel using microwave assisted methane plasma decomposition on catalyst | |
JP7030820B2 (en) | Method for producing hydrogen cyanide | |
JP2011529498A5 (en) | ||
JP2010527949A5 (en) | ||
KR100711349B1 (en) | Manufacturing method for syngas using tri-reforming reaction | |
TWI450861B (en) | Process for preparing hydrogen cyanide over a particulate heat transferrer conducted cyclically as a transported fluidized bed | |
US20140103259A1 (en) | Multi-tubular steam reformer and process for catalytic steam reforming of a hydrocarbonaceous feedstock | |
US20110002836A1 (en) | Method for Manufacturing Nitric Acid | |
CA1134593A (en) | Process for producing hydrogen cyanide | |
JP5485242B2 (en) | Coke removal at IN-SITU | |
US11192843B2 (en) | Process for producing methanol | |
NL2030905B1 (en) | Hybrid ammonia decomposition system | |
RU2643542C1 (en) | Method of obtaining hydrogen from hydrocarbon feedstock | |
US1934610A (en) | Process of producing hydrogen cyanide | |
US20100327231A1 (en) | Method of producing synthesis gas | |
KR101761829B1 (en) | Preparing method of synthesis gas and carbon monoxide | |
TWI501920B (en) | Production method and apparatus for hydrogen | |
KR20170125073A (en) | Online Furnace Drying Method for Thermal Isolation Catalytic Oxidation Furnace of Natural Gas | |
US6238634B1 (en) | Process for the nondestructive heating and supply of hot ammonia or hot ammonia containing feed gas | |
JPS5950602B2 (en) | Manufacturing method of cyanate compound | |
JP5288026B2 (en) | Method for producing carbonyl fluoride | |
Sun et al. | Methane cracking over a chinese coal char in a fixed-bed reactor | |
KR20010049667A (en) | B/d process for preparing hydrogen cyanide from nitric oxide and methane | |
WO2023247915A1 (en) | Process for cracking ammonia |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200924 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20210719 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210726 |
|
A601 | Written request for extension of time |
Free format text: JAPANESE INTERMEDIATE CODE: A601 Effective date: 20211026 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20211217 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20220207 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20220222 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7030820 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |